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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Advances and challenges for experiment and theory for multi-electron multi-proton transfer at electrified solid–liquid interfaces

Multi-electron, multi-proton transfer is important in a wide spectrum of processes spanning biological, chemical and physical systems. These reactions have attracted significant interest due to both fundamental curiosity and potential applications in energy technology. In this Perspective Review, we shed light on modern aspects of electrode processes in the 21st century, in particular on the recent advances and challenges in multistep electron/proton transfers at solid–liquid interfaces. Ongoing developments of analytical techniques and operando spectrometry at electrode/electrolyte interfaces and reliable computational approaches to simulate complicated interfacial electrochemical reactions enable us to obtain microscopic insights about these complex processes, such as the role of quantum effects in electrochemical reactions. Our motivation in this Perspective Review is to provide a comprehensive survey and discussion of state-of-the-art developments in experiments, materials, and theories for modern electrode process science, as well as to present an outlook for the future directions in this field.

Sakaushi, Ken↗
DOE OSTI2020

Chapter Twelve - Proton transfer and drug binding details revealed in neutron diffraction studies of wild-type and drug resistant HIV-1 protease

HIV-1 protease is an essential therapeutic target for the design and development of antiviral inhibitors to treat AIDS. We used room temperature neutron crystallography to accurately determine hydrogen atom positions in several protease complexes with clinical drugs, amprenavir and darunavir. Hydrogen bonding interactions were carefully mapped to provide an unprecedented picture of drug binding to the protease target. We demonstrate that hydrogen atom positions within the enzyme catalytic site can be altered by introducing drug resistant mutations and by protonating surface residues that trigger proton transfer reactions between the catalytic Asp residues and the hydroxyl group of darunavir. When protein perdeuteration is not feasible, we validate the use of initial H/D exchange with unfolded protein and partial deuteration in pure D2O with hydrogenous glycerol to maximize deuterium incorporation into the protein, with no detrimental effects on the growth of quality crystals suitable for neutron diffraction experiments.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy

Excited state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specic and enables direct, individual probes of the proton donating and accepting atoms. Here, we report a computational study to resolve the ESIPT in 10-Hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound, using time-dependent density functional theory combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Overall, our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge paving the way for future experiments at X-ray free electron lasers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Fast Proton Transfer and Hydrogen Evolution Reactivity Mediated by [Co 13 C 2 (CO) 24 ] 4–

A common approach to speeding up proton transfer (PT) by molecular catalysts is manipulation of the secondary coordina-tion sphere with proton relays and these enhance overall reaction rates by orders of magnitude. In contrast, heterogenous electrocatalysts have band structures that promote facile PT concerted with electron transfer (ET), known as the Volmer mechanism. Here in this paper, we show that [Co 13 C 2 (CO) 24 ] 4– , containing multiple Co-Co bonds to statistically enhance observed rates of PT, promotes PT on the order of 2.3 × 10 9 M -1 s -1 which suggests a diffusion-limited rate. The fast ET and PT chemistry is at-tributed to the delocalized electronic structure of [Co 13 C 2 (CO) 24 ] 4– . Electrochemical characterization of [Co 13 C 2 (CO) 24 ] 4– in the presence and absence of protons reveals ET kinetics and diffusion behavior similar to other small clusters such as nano-materials and fullerenes.

08 HYDROGEN↗
DOE OSTI2025

Redox‐Active Frustrated Lewis Pair‐Mediated B—H Bond Activation: From Proton Transfer to THF Ring Opening

The CAAC-stabilized dithiolene (L 0 ) zwitterion (1), an unusual redox-active intramolecular frustrated Lewis pair (FLP), activates the B─H bond of boranes via hydride-coupled reverse electron transfer processes. The reactions of 1 with catecholborane in THF give a zwitterionic bis(dithiolene)-based spiroborate ( 2 ), in which one sulphur atom (at the C2 carbon) bonds to the (CH 2 ) 4 OB(O) 2 C 6 H 4 chain due to the catecholborane (CatBH)/S thiourea Lewis pair-mediated THF ring opening. In addition to 2 , [CAAC(H)] + [(Cat) 2 B] − , ( 3 ), CAAC(H) 2 , ( 4 ), and [CAAC(H) 3 ] + [(Cat) 2 B] − , ( 5 ), are also isolated from these reactions. In addition to synthetic, structural, and spectroscopic data, a plausible reaction mechanism is proposed. This finding provides compelling experimental evidence of FLP-mediated B─H activation via net proton transfer.

carbenes↗
DOE OSTI2021

Tuning Proton Transfer Thermodynamics in SARS-CoV-2 Main Protease: Implications for Catalysis and Inhibitor Design

The catalytic reaction in SARS-CoV-2 main protease is activated by a proton transfer (PT) from Cys145 to His41. The same PT is likely also required for the covalent binding of some inhibitors. Here we use a multiscale computational approach to investigate the PT thermodynamics in the apo enzyme and in complex with two potent inhibitors, N3 and the α-ketoamide 13b. We show that with the inhibitors the free energy cost to reach the charge-separated state of the active-site dyad is lower, with N3 inducing the most significant reduction. We also show that a few key sites (including specific water molecules) significantly enhance or reduce the thermodynamic feasibility of the PT reaction, with selective desolvation of the active site playing a crucial role. The approach presented is a cost-effective procedure to identify the enzyme regions that control the activation of the catalytic reaction and is thus also useful to guide the design of inhibitors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cobalt Carbonyl Clusters Enable Independent Control of Two Proton Transfer Rates in the Mechanism for Hydrogen Evolution

Abstract Metal carbonyl clusters (MCC's) are atomically defined nanomaterials which can be characterized using the precise tools of molecular (electro)chemistry. HER mechanisms involve two proton transfer (PT) steps in the catalytic cycle. For HER catalyzed by [Co 11 C 2 (CO) 23 ] 3− ( 1 3− ), cyclic voltammetry measurements were used to determine the rate for PT1 as k PT1 =3×10 8 M −1 s −1 , whereas the rate for PT2 is k PT2 =3.7×10 3 M −1 s −1 . The fast, diffusion‐limited rate for PT1 is consistent with a previous report describing [Co 13 C 2 (CO) 24 ] 4− ( 2 4− ), with PT=2.9×10 9 M −1 s −1 . In both cases rate enhancement in PT1 is promoted by the many Co−Co bonds on the surface of the MCC that serve as PT sites: a statistical enhancement of rate akin to the effects of proton relays. In contrast, k PT2 varies and is five orders of magnitude slower for 1 2− compared with 2 4− . Thus, MCC's and nanomaterials offer an opportunity to enhance the rate for PT1 while maintaining thermochemical or kinetic control of PT2.

Pattanayak, Santanu↗
DOE OSTI2020

The crystal structures of a chloride-pumping microbial rhodopsin and its proton-pumping mutant illuminate proton transfer determinants

Microbial rhodopsins are versatile and ubiquitous retinal-binding proteins that function as light-driven ion pumps, light-gated ion channels, and photosensors, with potential utility as optogenetic tools for altering membrane potential in target cells. Insights from crystal structures have been central for understanding proton, sodium, and chloride transport mechanisms of microbial rhodopsins. Two of three known groups of anion pumps, the archaeal halorhodopsins (HRs) and bacterial chloride-pumping rhodopsins, have been structurally characterized. Here we report the structure of a representative of a recently discovered third group consisting of cyanobacterial chloride and sulfate ion-pumping rhodopsins, the Mastigocladopsis repens rhodopsin (MastR). Chloride-pumping MastR contains in its ion transport pathway a unique Thr-Ser-Asp (TSD) motif, which is involved in the binding of a chloride ion. The structure reveals that the chloride-binding mode is more similar to HRs than chloride-pumping rhodopsins, but the overall structure most closely resembles bacteriorhodopsin (BR), an archaeal proton pump. The MastR structure shows a trimer arrangement reminiscent of BR-like proton pumps and shows features at the extracellular side more similar to BR than the other chloride pumps. We further solved the structure of the MastR-T74D mutant, which contains a single amino acid replacement in the TSD motif. We provide insights into why this point mutation can convert the MastR chloride pump into a proton pump but cannot in HRs. Our study points at the importance of precise coordination and exact location of the water molecule in the active center of proton pumps, which serves as a bridge for the key proton transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Isoenergetic two-photon excitation enhances solvent-to-solute excited-state proton transfer

Two-photon excitation (TPE) is an attractive means for controlling chemistry in both space and time. Since isoenergetic one- and twophoton excitations (OPE and TPE) in non-centrosymmetric molecules are allowed to reach the same excited state, it is usually assumed that they produce similar excited-state reactivity. We compare the solvent-to-solute excited-state proton transfer of the super photobase FR0-SB following isoenergetic OPE and TPE. We find up to 62% increased reactivity following TPE compared to OPE. From steady-state spectroscopy, we rule out the involvement of different excited states and find that OPE and TPE spectra are identical in non-polar solvents but not in polar ones. We propose that differences in the matrix elements that contribute to the two-photon absorption cross sections lead to the observed enhanced isoenergetic reactivity, consistent with the predictions of our high-level coupledcluster-based computational protocol. We find that polar solvent configurations favor greater dipole moment change between ground and excited states, which enters the probability for TPE as the absolute value squared. This, in turn, causes a difference in the Franck– Condon region reached via TPE compared to OPE. We conclude that a new method has been found for controlling chemical reactivity via the matrix elements that affect two-photon cross sections, which may be of great utility for spatial and temporal precision chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Catalytic 1,3-Proton Transfer in Alkenes Enabled by Fe=NR Bond Cooperativity: A Strategy for p K a -Dictated Regioselective Transposition of C=C Double Bonds

Transition metal catalyzed alkene double bond transposition usually involves metal hydride intermediates. Despite significant advances in the design of catalysts that dictate product selectivity, control over substrate selectivity is less advanced and transition metal catalysts that selectively transpose double bonds in substrates containing multiple 1-alkene functionalities are rare. Herein, we report that the three-coordinate high spin (S = 2) Fe(II) imido complex [Ph 2 B( t BuIm) 2 Fe=NDipp][K(18-C-6)THF 2 ] (1-K(18-C-6)) catalyzes 1,3-proton transfer from 1-alkene substrates to afford 2-alkene transposition products. Mechanistic investigations involving kinetics, competition, and isotope labeling studies, supported by experimentally calibrated DFT computations, strongly support an unusual nonhydridic mechanism for alkene transposition that is enabled by the cooperative action of the iron center and basic imido ligand. As dictated by the pK a of the allylic protons, this catalyst enables the regioselective transposition of C=C double bonds in substrates containing multiple 1-alkenes. The high spin (S = 2) state of the complex allows a wide scope of functional groups to be tolerated, including those that are typical catalyst poisons, such as amines, N-heterocycles, and phosphines. Furthermore, these results demonstrate a new strategy for metal-catalyzed alkene transposition with predictable substrate regioselectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Stabilization of Hydroxide Ions at the Interface of a Hydrophobic Monolayer on Water via Reduced Proton Transfer

We report a joint study using surface-specific sum-frequency vibrational spectroscopy and ab initio molecular dynamics simulations, respectively, on a pristine hydrophobic (sub)monolayer hexane-water interface, namely, the hexane/water interface with varied vapor pressures of hexane and different pHs in water. We show clear evidence that hexane on water revises the interfacial water structure in a way that stabilizes the hypercoordinated solvation structure and slows down the migration of hydroxide ion (OH – ) relative to that in bulk water. Furthermore, this mechanism effectively attracts the OH – to the water-hydrophobic interface with respect to its counterion. The result illustrates the striking difference of proton transfer of hydrated OH – at the interface and in the bulk, which is responsible for the intrinsic charging effect at the hydrophobic interface.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Microcanonical Kinetics of Water-Mediated Proton Transfer in 4ABAH + ·(H 2 O) n = 4–6 Clusters (ABA = Aminobenzoic Acid): A Model System for Size-Dependent Relaxation to Ergodic Behavior

Here, we leverage the unique properties of the 4ABAH + · (H 2 O) n clusters (ABA = 4-aminobenzoic acid, n = 4−6) to quantitatively address how a finite, isolated system evolves into an ergodic condition starting from localized arrangements in configuration space. This system adopts two distinct structural isomers in which water molecules cluster around the cationic centers of its two protomers with widely separated positive charge centers. These isomers arise from excess proton attachment to either the acid (O) or amino (N) group on opposite sides of the benzene ring. Both forms are captured and kinetically trapped using cryogenic ion methods and then selectively vibrationally excited through their mutually exclusive IR bands involving NH and OH stretching fundamentals. Because the IR excitation lies below the water binding energy, the system can evolve to explore slow, rare events that lead to the interconversion between the two isomers. The rates of these intracluster reactions are determined by using a pump−probe scheme involving ∼5 ns IR pump and UV probe lasers. The rates occur on the microsecond time scale, leading to steady state populations of the isomers, thus revealing the cluster size-dependent fractionation between the two species at microcanonical equilibrium. The steady state distributions are correlated with the expected trend in the cluster size-dependent reaction energetics, which are in turn consistent with changes in the relative densities of states of the two species. These results thus provide an unusually clear example in which complex, protic-solvent-mediated chemical transformations are captured within a finite system at a precisely determined internal energy.

Rana, Abhijit [Yale Univ., New Haven, CT (United S↗